FIELD OF THE INVENTION
[0001] Laundry pretreatment methods and compositions used therein.
BACKGROUND OF THE INVENTION
[0002] Often, non-surfactant benefit agents are formulated into laundry pretreat compositions.
Such benefit agents include technologies such as hueing dyes, enzymes, brighteners,
soil release polymers, chelants and mixtures thereof. However, upon addition of the
pretreated fabric to the wash liquor such benefit agents can exhibit poor dispersion
characteristics and so form localized areas of high concentration of said ingredients
on the fabric.
[0003] This has the negative effect of reducing the effectiveness of the benefit agent to
provide to all the fabrics present in the wash liquor and so negatively affect the
consumer wash experience. In the case of benefit agents such as hueing dyes, this
localized high concentration can also causing localized spot staining on fabrics.
This staining is a result of the high concentration of hueing dye in contact with
a particular area of fabric.
[0004] Thus, there is a need in the art for the provision of a laundry pretreatment composition
comprising non-surfactant benefit agents, which exhibits reduced localized high concentrations
of said benefit agents in the wash liquor.
[0005] The Inventors surprisingly found that the compositions of the present invention exhibited
improved dispersion of benefit agents in the wash liquor and reduced instances of
localized high concentrations of said actives in the wash liquor.
SUMMARY OF THE INVENTION
[0006] The present invention is to a method of laundering a fabric comprising the steps
of;
a. Applying a laundry pretreat composition to a stain on a fabric in a pretreat step;
b. Washing the fabric from step (a) in an automatic or semiautomatic washing machine
or in a hand wash operation;
wherein said laundry pretreatment composition comprises;
- i. Between 0.0001% and 8% by weight of the composition of a non-surfactant benefit
agent;
- ii. Between 40% and 80% by weight of the composition of an alkoxylated alkyl surfactant
system, wherein the alkoxylated alkyl surfactant comprise a first alkoxylated alkyl
surfactant and a second alkoxylated alkyl surfactant, wherein;
- I. the first surfactant has the general structure R-A, where R is a linear or branched
alkyl chain having a chain length of between 6 and 18 carbon atoms, A is at least
one alkoxy group having an average degree of alkoxylation of between 2 and 12 and
wherein the alkoxy groups consist of identical repeat alkoxy groups or identical repeat
alkoxy group blocks wherein a block comprises at least two alkoxy groups;
- II. the second surfactant has the general structure R'-E-C, wherein R' is a linear
or branched alkyl chain having a chain length of between 6 and 18 carbon atoms, E
is an ethoxy chain consisting of between 2 and 12 ethoxy groups and C is an end cap,
wherein the end cap is selected from;
- a. an alkyl chain consisting of between 1 and 8 alkoxy groups selected from propoxy
groups, butoxy groups and a mixture thereof; or
- b. an -OH group; or
- c. a linear or branched alkyl chain of the general formula R" wherein R" consists
of between 1 and 8 carbon atoms;
- d. or a mixture thereof;
- iii. Between 0% and 40% by weight of the composition of a solvent, wherein the solvent
is selected from polar protic solvents, polar aprotic solvents or a mixture thereof.
DETAILED DESCRIPTION OF THE INVENTION
Pretreatment method
[0007] The present invention is to a method of laundering a fabric comprising the steps
of;
a. Applying a laundry pretreat composition to a stain on a fabric in a pretreat step;
b. Washing the fabric from step (a) in an automatic or semi-automatic washing machine
or in a hand wash operation.
[0008] The pretreat composition in step (a) can be added directly to the fabric in an undiluted
form. Any suitable means can be used to apply it, including pouring, scooping, brushing,
rubbing or mixtures thereof. Those skilled in the art will recognize suitable means.
[0009] The pretreat composition in step (a) can be first diluted in a quantity of water
and then added to the fabric using the same means as described above. Those skilled
in the art will be aware of suitable means to dilute and suitable dilution concentrations
to use.
[0010] Those skilled in the art will be aware of suitable means to launder fabrics in step
(b). The fabric may be laundered directly after pretreating in step (a) with the addition
of no further cleaning compositions. Alternatively, a separate fabric detergent composition
in any suitable form may be used.
Laundry pretreatment composition
[0011] The laundry pretreatment composition may be any suitable composition. The composition
may be in the form of a solid, a liquid, or a mixture thereof.
[0012] A solid can be in the form of free flowing particulates, compacted solids or a mixture
thereof. It should be understood, that a solid may comprise some water, but is essentially
free of water. In other words, no water is intentionally added other than what comes
from the addition of various raw materials.
[0013] In relation to the laundry pretreatment composition of the present invention, the
term 'liquid' encompasses forms such as dispersions, gels, pastes and the like. The
liquid composition may also include gases in suitably subdivided form. The term 'liquid
laundry pretreatment composition' refers to any laundry detergent composition comprising
a liquid capable of wetting and treating fabric e.g., cleaning clothing in a domestic
washing machine. A dispersion for example is a liquid comprising solid or particulate
matter contained therein.
[0014] The laundry treatment composition comprises between 0.0001% and 8% by weight of the
composition of a non-surfactant benefit agent. The non-surfactant benefit agent is
described in more detail below.
[0015] The laundry treatment composition comprises between 40% and 80% by weight of the
composition of an alkoxylated alkyl surfactant system. The alkoxylated alkyl surfactant
is described in more detail below.
[0016] The laundry treatment composition comprises between 0% and 40% by weight of the composition
of a solvent, wherein the solvent is selected from polar protic solvents, polar aprotic
solvents or a mixture thereof. The solvent is described in more detail below.
[0017] Without wishing to be bound by theory, it is believed that the non-surfactant benefit
agent complexes with the alkoxylated alkyl surfactant to form a micellar structure.
In the form of these micelle structure, the non-surfactant benefit agent is better
dispersed in the wash liquor and less likely to form areas of high localized concentration.
Non-surfactant benefit agent
[0018] By 'non-surfactant benefit agent' we herein mean any compound that provides a benefit
to the fabrics, such as cleaning, freshness, aesthetics or the like, and that does
not exhibit surfactant properties. Surfactants are organic molecules with a hydrophobic
tail (Alkyl-like which is oil soluble) and a hydrophilic part (water soluble). Surfactants
exhibit the ability to lower surface tension and can form micelles and other phases
such as hexagonal.
[0019] The liquid composition comprises between 0.0001% and 8% by weight of the composition
of a non-surfactant benefit agent. The liquid composition may comprise between 0.0005%
and 6% or even between 0.001% and 5% by weight of the composition of the non-surfactant
benefit agent.
[0020] The non-surfactant benefit agent may be any suitable non-surfactant benefit agent.
Those skilled in the art would recognize suitable non-surfactant benefit agents.
[0021] Preferably, the non-surfactant benefit agent has a hydrophilic index of between 6
and 16, more preferably between 8 and 14. Where there is a mixture of non-surfactant
benefit agents, each benefit agent may have a hydrophilic index of between 6 and 16,
more preferably between 8 and 14. Alternatively, the mixture of benefit agents taken
together may have a hydrophilic index of between 6 and 16, more preferably between
8 and 14. Those skilled in the art will know how to calculate the hydrophilic index
using well known equations.
[0022] The hydrophilic index of a non-surfactant benefit agent (HI
NS) can be calculated as follows;

Those skilled in the art will know how to recognize the hydrophilic part and calculate
the appropriate molecular weights (MW).
[0023] The hydrophilic index of a mixed non-surfactant benefit agent system (HI
MNS) containing y non-surfactant benefit agents can be calculated as follows;

[0024] For the purpose of the present invention, the following groups should be understood
to be hydrophilic groups; -OH of an alcohol, CH
2CH
2O from an ethoxylate, CH
2CH(O)CH
2O of glycerol groups, sulphates, sulphonates, carbonates and carboxylates. The molecular
weight of these in both the hydrophilic part and the overall molecule should be determined
in the absence the counterion, for example -SO
3-, -CO
2- and not SO
3Na, SO
3H, CO
2H or CO
2Na. With respect to quaternary ammonium compounds, an N
+R
4 groups are recognized as hydrophilic groups and should be interpreted for hydrophilic
index calculations as an N
+(CH
2)
4 group regardless of what the R
1-4 substitutions are. An ether is not recognized as a hydrophilic group unless said
ether is an ethoxylate as described above. All other groups are not recognized as
hydrophilic groups in relation to the present invention.
[0025] Preferably, the non-surfactant benefit agent is alkoxylated, more preferably ethoxylated.
[0026] The non-surfactant benefit agent may be selected from the group comprising hueing
dyes, brighteners, soil release polymers, chelants and mixtures thereof. Preferably,
the benefit agent is a hueing dye.
[0027] The hueing dye (sometimes referred to as shading, bluing or whitening agents) typically
provides a blue or violet shade to fabric. Hueing dyes can be used either alone or
in combination to create a specific shade of hueing and/or to shade different fabric
types. This may be provided for example by mixing a red and green-blue dye to yield
a blue or violet shade. Preferably the hueing dye is a blue or violet hueing dye,
providing a blue or violet color to a white cloth or fabric. Such a white cloth treated
with the composition will have a hue angle of 240 to 345, more preferably 260 to 325,
even more preferably 270 to 310.
[0028] In one aspect, a hueing dye suitable for use in the present invention has, in the
wavelength range about 750 nm, in methanol solution, a maximum extinction coefficient
greater than about 1000 liter/mol/cm. In one aspect, a hueing dye suitable for use
in the present invention has, in the wavelength range of about 540 nm to about 630
nm, a maximum extinction coefficient from about 10,000 to about 100,000 liter/mol/cm.
In one aspect, a hueing dye suitable for use in the present invention has, in the
wavelength range of about 560 nm to about 610 nm, a maximum extinction coefficient
from about 20,000 to about 70,000 liter/mol/cm or even about 90,000 liter/mol/cm.
[0029] The Test Methods provided below can be used to determine if a dye, or a mixture of
dyes, is a hueing dye for the purposes of the present invention.
Test Methods
I. Method for Determining Deposition for a Dye
[0030]
a.) Unbrightened Multifiber Fabric Style 41 swatches (MFF41, 5cm x 10cm, average weight
1.46g) serged with unbrightened thread are purchased from Testfabrics, Inc. (West
Pittston, PA). MFF41 swatches are stripped prior to use by washing two full cycles
in AATCC heavy duty liquid laundry detergent (HDL) nil brightener at 49°C and washing
3 additional full cycles at 49°C without detergent. Four replicate swatches are placed
into each flask.
b.) A sufficient volume of AATCC standard nil brightener HDL detergent solution is
prepared by dissolving the detergent in 0 gpg water at room temperature at a concentration
of 1.55 g per liter.
c.) A concentrated stock solution of dye is prepared in an appropriate solvent selected
from dimethyl sulfoxide (DMSO), ethanol or 50:50 ethanol:water. Ethanol is preferred.
The dye stock is added to a beaker containing 400mL detergent solution (prepared in
step I.b. above) in an amount sufficient to produce an aqueous solution absorbance
at the λmax of 0.1 AU (± 0.01AU) in a cuvette of path length 1.0 cm. For a mixture of dyes, the
sum of the aqueous solution absorbance at the λmax of the individual dyes is 0.1 AU (± 0.01AU) in a cuvette of path length 1.0 cm. Total
organic solvent concentration in a wash solution from the concentrated stock solution
is less than 0.5%. A 125mL aliquot of the wash solution is placed into 3 separate
disposable 250mL Erlenmeyer flasks (Thermo Fisher Scientific, Rochester, NY).
d.) Four MFF41 swatches are placed into each flask, flasks are capped and manually
shaken to wet the swatches. Flasks are placed onto a Model 75 wrist action shaker
from Burrell Scientific, Inc. (Pittsburg, PA) and agitated on the highest setting
of 10 (390 oscillations per minute with an arc of 14.6°). After 12 minutes, the wash
solution is removed by vacuum aspiration, 125mL of 0gpg water is added for a rinse,
and the flasks agitated for 4 additional minutes. Rinse solution is removed by vacuum
aspiration and swatches are spun in a Mini Countertop Spin Dryer (The Laundry Alternative
Inc., Nashua, NH) for 5 minutes, after which they are allowed to air dry in the dark.
e.) L*, a*, and b* values for the 3 most consumer relevant fabric types, cotton and
polyester, are measured on the dry swatches using a LabScan XE reflectance spectrophotometer
(HunterLabs, Reston, VA; D65 illumination, 10° observer, UV light excluded). The L*,
a*, and b* values of the 12 swatches (3 flasks each containing 4 swatches) are averaged
and the hueing deposition (HD) of the dye is calculated for each fabric type using
the following equation:

wherein the subscripts c and s respectively refer to the control, i.e., the fabric
washed in detergent with no dye, and the fabric washed in detergent containing dye,
or a mixture of dyes, according to the method described above.
II. Method for Determining Relative Hue Angle (vs. Nil Dye Control)
III. Method to Determine if a Dye is a Hueing Dye
[0032] A dye, or mixture of dyes, is considered a hueing dye (also known as a shading or
bluing dye) for the purposes of the present invention if (a) either the HD
cotton or the HD
polyester is greater than or equal to 2.0 DE* units or preferably greater than or equal to
3.0, or 4.0 or even 5.0, according to the formula above, and (b) the relative hue
angle (see Method III. below) on the fabric that meets the DE* criterion in (a) is
within 240 to 345, more preferably 260 to 325, even more preferably 270 to 310. If
the value of HD for both fabric types is less than 2.0 DE* units, or if the relative
hue angle is not within the prescribed range on each fabric for which the DE* meets
the criteria the dye is not a hueing dye for the purposes of the present invention.
[0033] The hueing dye may be selected from any chemical class of dye as known in the art,
including but not limited to acridine, anthraquinone (including polycyclic quinones),
azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), benzodifurane,
benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane,
formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro,
nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane,
xanthenes and mixtures thereof.
[0034] Suitable hueing dyes include small molecule dyes, polymeric dyes and dye-clay conjugates.
Preferred hueing dyes are selected from small molecule dyes and polymeric dyes.
[0035] Suitable small molecule dyes may be selected from the group consisting of dyes falling
into the
Colour Index (C.I., Society of Dyers and Colourists, Bradford, UK) classifications of Acid, Direct, Basic, Reactive, Solvent or Disperse dyes. Preferably
such dyes can be classified as Blue, Violet, Red, Green or Black, and provide the
desired shade either alone or in combination with other dyes or in combination with
other adjunct ingredients. Reactive dyes may contain small amounts of hydrolyzed dye
as sourced, and in detergent formulations or in the wash may undergo additional hydrolysis.
Such hydrolyzed dyes and mixtures may also serve as suitable small molecule dyes.
[0036] In another aspect, dyes may include those selected from the group consisting of dyes
denoted by the Colour Index designations such as Direct Violet 5, 7, 9, 11, 31, 35,
48, 51, 66, and 99, Direct Blue 1, 71, 80 and 279, Acid Red 17, 73, 52, 88 and 150,
Acid Violet 15, 17, 24, 43, 49 and 50, Acid Blue 15, 17, 25, 29, 40, 45, 48, 75, 80,
83, 90 and 113, Acid Black 1, Basic Violet 1, 3, 4, 10 and 35, Basic Blue 3, 16, 22,
47, 66, 75 and 159, anthraquinone Disperse or Solvent dyes such as Solvent Violet
11, 13, 14, 15, 15, 26, 28, 29, 30, 31, 32, 33, 34, 26, 37, 38, 40, 41, 42, 45, 48,
59; Solvent Blue 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22,35,36,40,41,45,59,59:1,
63, 65, 68, 69, 78, 90; Disperse Violet 1, 4, 8, 11, 11:1, 14, 15, 17, 22, 26, 27,
28, 29, 34, 35, 36, 38, 41, 44, 46, 47, 51, 56, 57, 59, 60, 61, 62, 64, 65, 67, 68,
70, 71, 72, 78, 79, 81, 83, 84, 85, 87, 89, 105; Disperse Blue 2, 3, 3:2, 8, 9, 13,
13:1, 14, 16, 17, 18, 19, 22, 23, 24, 26, 27, 28, 31, 32, 34, 35, 40, 45, 52, 53,
54, 55, 56, 60, 61, 62, 64, 65, 68, 70, 72, 73, 76, 77, 80, 81, 83, 84, 86, 87, 89,
91, 93, 95, 97, 98, 103, 104, 105, 107, 108, 109, 11, 112, 113, 114, 115, 116, 117,
118, 119, 123, 126, 127, 131, 132, 134, 136, 140, 141, 144, 145, 147, 150, 151, 152,
153, 154, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 168, 169, 170, 176,
179, 180, 180:1, 181, 182, 184, 185, 190, 191, 192, 196, 197, 198, 199, 203, 204,
213, 214, 215, 216, 217, 218, 223, 226, 227, 228, 229, 230, 231, 232, 234, 235, 236,
237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 249, 252, 261, 262, 263, 271,
272, 273, 274, 275, 276, 277, 289, 282, 288, 289, 292, 293, 296, 297, 298, 299, 300,
302, 306, 307, 308, 309, 310, 311, 312, 314, 318, 320, 323, 325, 326, 327, 331, 332,
334, 347, 350, 359, 361, 363, 372, 377 and 379, azo Disperse dyes such as Disperse
Blue 10, 11, 12, 21, 30, 33, 36, 38, 42, 43, 44,47,79,79:1,79:2,79:3, 82, 85, 88,
90, 94, 96, 100, 101, 102, 106, 106:1, 121, 122, 124, 125, 128, 130, 133, 137, 138,
139, 142, 146, 148, 149, 165, 165:1, 165:2, 165:3, 171, 173, 174, 175, 177, 183, 187,
189, 193, 194, 200, 201, 202, 206, 207, 209, 210, 211, 212, 219, 220, 224, 225, 248,
252, 253, 254, 255, 256, 257, 258, 259, 260, 264, 265, 266, 267, 268, 269, 270, 278,
279, 281, 283, 284, 285, 286, 287, 290, 291, 294, 295, 301, 304, 313, 315, 316, 317:319,
321, 322, 324, 328, 330, 333, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345,
346, 351, 352, 353, 355, 356, 358, 360, 366, 367, 368, 369, 371, 373, 374, 375, 376
and 378, Disperse Violet 2, 3, 5, 6, 7, 9, 10, 12, 3, 16, 24, 25,33,39, 42, 43, 45,
48, 49, 50, 53, 54, 55, 58, 60, 63, 66, 69, 75, 76, 77, 82, 86, 88, 91, 92, 93, 93:1,
94, 95, 96, 97, 98, 99, 100, 102, 104, 106 and 107. Preferably, small molecule dyes
can be selected from the group consisting of C. I. numbers Acid Violet 17, Acid Blue
80, Acid Violet 50, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88,
Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
[0037] In another aspect suitable small molecule dyes may include dyes with CAS-No's 52583-54-7,
42783-06-2, 210758-04-6, 104366-25-8,122063-39-2,167940-11-6,52239-04-0, 105076-77-5,84425-43-4,
and 87606-56-2, and non-azo dyes Disperse Blue 250, 354, 364, Solvent Violet 8, Solvent
blue 43, 57, Lumogen F Blau 650, and Lumogen F Violet 570.
[0038] In another aspect suitable small molecule dyes include azo dyes, preferably mono-azo
dyes, covalently bound to phthalocyanine moieties, preferably Al- and Si-phthalocyanine
moieties, via an organic linking moiety.
[0039] Suitable polymeric dyes include dyes selected from the group consisting of polymers
containing covalently bound (sometimes referred to as conjugated) chromogens, (also
known as dye-polymer conjugates), for example polymers with chromogen monomers co-polymerized
into the backbone of the polymer and mixtures thereof.
[0040] Polymeric dyes include: (a) Reactive dyes bound to water soluble polyester polymers
via at least one and preferably two free OH groups on the water soluble polyester
polymer. The water soluble polyester polymers can be comprised of comonomers of a
phenyl dicarboxylate, an oxyalkyleneoxy and a polyoxyalkyleneoxy; (b) Reactive dyes
bound to polyamines which are polyalkylamines that are generally linear or branched.
The amines in the polymer may be primary, secondary and/or tertiary. Polyethyleneimine
in one aspect is preferred. In another aspect, the polyamines are ethoxylated; (c)
Dye polymers having dye moieties carrying negatively charged groups obtainable by
copolymerization of an alkene bound to a dye containing an anionic group and one or
more further alkene comonomers not bound to a dye moiety; (d) Dye polymers having
dye moieties carrying positively charged groups obtainable by copolymerization of
an alkene bound to a dye containing an cationic group and one or more further alkene
comonomers not bound to a dye moiety; (e) Polymeric thiophene azo polyoxyalkylene
dyes containing carboxylate groups; and (f) dye polymer conjugates comprising at least
one reactive dye and a polymer comprising a moiety selected from the group consisting
of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety
and combinations thereof; said polymers preferably selected from the group consisting
of polysaccharides, proteins, polyalkyleneimines, polyamides, polyols, and silicones.
In one aspect, carboxymethyl cellulose (CMC) may be covalently bound to one or more
reactive blue, reactive violet or reactive red dye such as CMC conjugated with C.I.
Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE,
product code S-ACMC.
[0041] Other suitable polymeric dyes include polymeric dyes selected from the group consisting
of alkoxylated triphenyl-methane polymeric colourants, alkoxylated carbocyclic and
alkoxylated heterocyclic azo colourants, including alkoxylated thiophene polymeric
colourants, and mixtures thereof. Preferred polymeric dyes comprise the optionally
substituted alkoxylated dyes, such as alkoxylated triphenyl-methane polymeric colourants,
alkoxylated carbocyclic and alkoxylated heterocyclic azo colourants including alkoxylated
thiophene polymeric colourants, and mixtures thereof, such as the fabric-substantive
colorants sold under the name of Liquitint® (Milliken, Spartanburg, South Carolina,
USA).
[0042] Suitable polymeric dyes are illustrated below. As with all such alkoxylated compounds,
the organic synthesis may produce a mixture of molecules having different degrees
of alkoxylation. During a typical ethoxylation process, for example, the randomness
of the ethylene oxide addition results in a mixture of oligomers with different degrees
of ethoxylation. As a consequence of its ethylene oxide number distribution, which
often follows a Poisson law, a commercial material contains substances with somewhat
different properties. For example, in one aspect, the polymeric dye resulting from
an ethoxylation is not a single compound containing five (CH
2CH
2O) units as the general structure (Formula A, with x+y = 5) may suggest. Instead,
the product is a mixture of several homologs whose total of ethylene oxide units varies
from about 2 to about 10. Industrially relevant processes will typically result in
such mixtures, which may normally be used directly to provide the hueing dye, or less
commonly may undergo a purification step.
[0043] Preferably, the hueing dye may be one wherein the hueing dye has the following structure:
Dye-(G)a-NR1R2,
wherein the -(G)a-NR
1R
2group is attached to an aromatic ring of the dye, G is independently -SO
2- or -C(O)-, the index a is an integer with a value of 0 or 1 and R
1 and R
2 are independently selected from H, a polyoxyalkylene chain, a C
1-8 alkyl, optionally the alkyl chains comprise ether (C-O-C), ester and/or amide links,
optionally the alkyl chains are substituted with -Cl, -Br, -CN, -NO
2, -SO
2CH
3, -OH and mixtures thereof, C
6-10 aryl, optionally substituted with a polyoxyalkylene chain, C
7-16 alkaryl optionally substituted with ether (C-O-C), ester and/or amide links, optionally
substituted with -Cl, -Br, -CN, -NO
2, -SO
2CH
3, -OH, polyoxyalkylene chain substituted C
1-8 alkyl, polyoxyalkylene chain substituted C
6-10 aryl, polyoxyalkylene chain substituted C
7-16 alkaryl and mixtures thereof; said polyoxyalkylene chains independently having from
about 2 to about 100, about 2 to about 50, about 3 to about 30 or about 4 to about
20 repeating units. Preferably, the repeating units are selected from the group consisting
of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. Preferably,
the repeating units are essentially ethylene oxide.
[0044] Preferably, the hueing dye may have the structure of Formula A:

wherein the index values x and y are independently selected from 1 to 10. In some
aspects, the average degree of ethoxylation, x + y, sometimes also referred to as
the average number of ethoxylate groups, is from about 3 to about12, preferably from
about 4 to about 8. In some embodiments the average degree of ethoxylation, x + y,
can be from about 5 to about 6. The range of ethoxylation present in the mixture varies
depending on the average number of ethoxylates incorporated. Typical distributions
for ethoxylation of toluidine with either 5 or 8 ethoxylates are shown in Table II
on
page 42 in the Journal of Chromatography A 1989, volume 462, pp. 39 -47. The whitening agents are synthesized according to the procedures disclosed in
U.S. Pat. No. 4,912,203 to Kluger et al.; a primary aromatic amine is reacted with an appropriate amount of ethylene oxide,
according to procedures well known in the art. The polyethyleneoxy substituted m-toluidine
useful in the preparation of the colorant can be prepared by a number of well known
methods. It is preferred, however, that the polyethyleneoxy groups be introduced into
the m-toluidine molecule by reaction of the m-toluidine with ethylene oxide. Generally
the reaction proceeds in two steps, the first being the formation of the corresponding
N,N-dihydroxyethyl substituted m-toluidine. In some aspects, no catalyst is utilized
in this first step (for example as disclosed at Column 4, lines 16-25 of
U.S. Pat. No. 3,927,044 to Foster et al.). The dihydroxyethyl substituted m-toluidine is then reacted with additional ethylene
oxide in the presence of a catalyst such as sodium (described in Preparation II of
U.S. Pat. No. 3,157,633 to Kuhn), or it may be reacted with additional ethylene oxide in the presence of sodium or
potassium hydroxide (described in Example 5 of
U.S. Pat. No. 5,071,440 to Hines et al.). The amount of ethylene oxide added to the reaction mixture determines the number
of ethyleneoxy groups which ultimately attach to the nitrogen atom. In some aspects,
an excess of the polyethyleneoxy substituted m-toluidine coupler may be employed in
the formation of the whitening agent and remain as a component in the final colorant
mixture. In certain aspects, the presence of excess coupler may confer advantageous
properties to a mixture in which it is incorporated such as the raw material, a pre-mix,
a finished product or even the wash solution prepared from the finished product.
[0045] The HI
NS for the dye of Formula A as a function of the index values x and y are given in the
table below.
Dye A(x+y) |
x + y |
MW of Dye |
MW of Hydrophilic Part |
HINS |
A2 |
2 |
369.44 |
90.12 |
4.9 |
A6 |
6 |
545.65 |
266.33 |
9.8 |
A10 |
10 |
721.86 |
442.54 |
12.3 |
[0046] The HI of a mixture of A2, A6 and A10 in a weight ratio of 30:30:40 is 9.3.
[0047] The hueing dye may preferably have the following structure:

wherein:
R1 and R2 are independently selected from the group consisting of: H; alkyl; alkoxy; alkyleneoxy;
alkyl capped alkyleneoxy; urea; and amido;
R3 is a substituted aryl group;
X is a substituted group comprising sulfonamide moiety and optionally an alkyl and/or
aryl moiety, and wherein the substituent group comprises at least one alkyleneoxy
chain.
[0048] The hueing dye may be a thiophene dye such as a thiophene azo dye, preferably alkoxylated.
Optionally the dye may be substituted with at least one solubilizing group selected
from sulphonic, carboxylic or quaternary ammonium groups.
[0050] Suitable dye clay conjugates include dye clay conjugates selected from the group
comprising at least one cationic/basic dye and a smectite clay; a preferred clay may
be selected from the group consisting of Montmorillonite clay, Hectorite clay, Saponite
clay and mixtures thereof. In another aspect, suitable dye clay conjugates include
dye clay conjugates selected from the group consisting of a clay and one cationic/basic
dye selected from the group consisting of C.I. Basic Yellow 1 through 108, C.I. Basic
Orange 1 through 69, C.I. Basic Red 1 through 118, C.I. Basic Violet 1 through 51,
C.I. Basic Blue 1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through
23, CI Basic Black 1 through 11 In still another aspect, suitable dye clay conjugates
include dye clay conjugates selected from the group consisting of: Montmorillonite
Basic Blue B7 C.I. 42595 conjugate, Montmorillonite Basic Blue B9 C.I. 52015 conjugate,
Montmorillonite Basic Violet V3 C.I. 42555 conjugate, Montmorillonite Basic Green
G1 C.I. 42040 conjugate, Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite
C.I. Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate, Hectorite
Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3 C.I. 42555 conjugate,
Hectorite Basic Green G1 C.I. 42040 conjugate, Hectorite Basic Red R1 C.I. 45160 conjugate,
Hectorite C.I. Basic Black 2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate,
Saponite Basic Blue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555 conjugate,
Saponite Basic Green G1 C.I. 42040 conjugate, Saponite Basic Red R1 C.I. 45160 conjugate,
Saponite C.I. Basic Black 2 conjugate and mixtures thereof.
[0051] Any suitable soil release polymer may be used. Those skilled in the art would recognise
suitable soil release polymers. The soil release polymer may comprise a polyester
soil release polymer. Suitable polyester soil release polymers may be selected from
terephthalate polymers, amine polymers or mixtures thereof. Suitable polyester soil
release polymers may have a structure as defined by one of the following structures
(I), (II) or (III):
(I) -[(OCHR
1-CHR
2)
a-O-OC-Ar-CO-]
d
(II) -[(OCHR
3-CHR
4)
b-O-OC-sAr-CO-]
e
(III) -[(OCHR
5-CHR
6)
c-OR
7]
f
wherein:
a, b and c are from 1 to 200;
d, e and f are from 1 to 50;
Ar is a 1,4-substituted phenylene;
sAr is 1,3-substituted phenylene substituted in position 5 with SO3Me;
Me is H, Na, Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium
wherein the alkyl groups are C1-C18 alkyl or C2-C10 hydroxyalkyl, or any mixture thereof; R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C18 n- or iso-alkyl; and R7 is a linear or branched C1-C18 alkyl, or a linear or branched C2-C30 alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group.
[0052] Suitable polyester soil release polymers may be terephthalate polymers having the
structure of formula (I) or (II) above.
[0053] Suitable polyester soil release polymers include the Repel-o-tex series of polymers
such as Repel-o-tex SF2 (Rhodia) and/or the Texcare series of polymers such as Texcare
SRA300 (Clariant).
[0054] Any suitable brightener may be used. Those skilled in the art would recognize suitable
brighteners. The brightener is preferably selected from stilbene brighteners.
[0055] The brightener may comprise stilbenes, such as brightener 15. Other suitable brighteners
include brightener 49. The brightener maybe in micronized particulate form, having
a weight average particle size in the range of from 3 to 30 micrometers, or from 3
micrometers to 20 micrometers, or from 3 to 10 micrometers. The brightener can be
alpha or beta crystalline form.
[0056] Suitable brighteners include: di-styryl biphenyl compounds, e.g. Tinopal® CBS-X,
di-amino stilbene di-sulfonic acid compounds, e.g. Tinopal® DMS pure Xtra and Blankophor®
HRH, and Pyrazoline compounds, e.g. Blankophor® SN, and coumarin compounds, e.g. Tinopal®
SWN.
[0057] Preferred brighteners are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole,
disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl)amino 1 ,3,5- triazin-2-yl)];amino}stilbene-2-2'
disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}
stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfostyryl)biphenyl. A suitable
fluorescent brightener is C.I. Fluorescent Brightener 260, which may be used in its
beta or alpha crystalline forms, or a mixture of these forms.
[0058] Any suitable chelant may be used. Those skilled in the art would recognize suitable
chelants. Suitable chelants maybe selected from: diethylene triamine pentaacetate,
diethylene triamine penta(methyl phosphonic acid), ethylene diamine-N'N'-disuccinic
acid, ethylene diamine tetraacetate, ethylene diamine tetra(methylene phosphonic acid),
hydroxyethane di(methylene phosphonic acid), and any combination thereof. A suitable
chelant is ethylene diamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic
acid (HEDP). The laundry treatment composition may comprise ethylene diamine-N'N'-
disuccinic acid or salt thereof. The ethylene diamine-N'N'-disuccinic acid maybe in
S,S enantiomeric form. The composition may comprise 4,5-dihydroxy-m-benzenedisulfonic
acid disodium salt, glutamic acid-N,N-diacetic acid (GLDA) and/or salts thereof, 2-hydroxypyridine-1-oxide,
Trilon P™ available from BASF, Ludwigshafen, Germany. Suitable chelants may also be
calcium carbonate crystal growth inhibitors. Suitable calcium carbonate crystal growth
inhibitors maybe selected from the group consisting of: 1-hydroxyethanediphosphonic
acid (HEDP) and salts thereof; N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and
salts thereof; 2-phosphonobutane-1,2,4-tricarboxylic acid and salts thereof; and any
combination thereof.
[0059] The composition may comprise a calcium carbonate crystal growth inhibitor, such as
one selected from the group consisting of: 1-hydroxyethanediphosphonic acid (HEDP)
and salts thereof; N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts thereof;
2-phosphonobutane-1,2,4-tricarboxylic acid and salts thereof; and any combination
thereof.
Alkoxylated alkyl surfactant
[0060] The liquid composition comprises between 40% and 80% by weight of the composition
of an alkoxylated alkyl surfactant system, wherein the alkoxylated alkyl surfactant
comprise a first alkoxylated alkyl surfactant and a second alkoxylated alkyl surfactant.
The liquid composition may comprise between 50% and 75% or even between 60% and 70%
by weight of the composition of the alkoxylated alkyl surfactant system.
[0061] The first surfactant has the general structure R-A, where R is a linear or branched
alkyl chain having a chain length of between 6 and 18 carbon atoms, A is at least
one alkoxy group having an average degree of alkoxylation of between 2 and 12 and
wherein the alkoxy group consists of identical repeat alkoxy groups or identical repeat
alkoxy group blocks wherein a block comprises at least two alkoxy groups.
[0062] The first surfactant may be an anionic surfactant, a non-ionic surfactant or a mixture
thereof. Preferably, the alkoxylated alkyl surfactant is a non-ionic alkoxylated alkyl
surfactant.
[0063] The alkoxy chain of the first surfactant may comprise an ethoxylate group, butoxylate
group, propoxylate group or a mixture thereof. The alkyl group of the first surfactant
consists of identical repeat alkoxy groups or identical repeat alkoxy group blocks
wherein a block comprises at least two alkoxy groups. For example, the alkoxy group
could be EO-EO-EO-EO (where an 'EO' is an ethoxy group), or the alkoxy group could
be the following repeat blocks [EO-BO]-[EO-BO]-]EO-BO] (where a 'BO' is an butoxy
group), or a further example being [BO-PO-EO]-[BO-PO-EO]-[BO-PO-EO]. Further examples
include the following repeat blocks [EO-PO] or [EO-EO-PO]. These are non-limiting
examples and the skilled person would be aware of further repeat alkoxy blocks or
repeat alkoxy groups.
[0064] The first surfactant is preferably selected from the group comprising fatty alcohol
alkoxylates, Guerbet alcohol alkoxylates, oxo alcohol alkoxylates, alkyl phenol alcohol
alkoxylates and mixtures thereof.
[0065] The alkyl chain of the first surfactant may comprise between 8 and 16 or even between
10 and 14 carbon atoms.
[0066] The average degree of alkoxylation of the first surfactant is preferably between
3 and 10, or even between 4 and 8.
[0067] Preferably, the first surfactant has a hydrophilic index of between 6 and 16, more
preferably between 8 and 14. Where the first surfactant is a mixture of alkoxylated
alkyl surfactants according to the definition of the first surfactant, each surfactant
in the mixture has a hydrophilic index of between 6 and 16, more preferably between
8 and 14. Alternatively, the mixture of alkoxylated alkyl surfactants taken together
may have a hydrophilic index of between 6 and 16, more preferably between 8 and 14.
Those skilled in the art will know how to calculate the hydrophilic index using well
known equations.
[0068] The hydrophilic index of a surfactant (HI
S) can be calculated as follows;

[0069] Those skilled in the art will know how to recognise the hydrophilic part and calculate
the appropriate molecular weights (MW).
[0070] The hydrophilic index of a mixed surfactant system (HI
MS) can be calculated as follows;

[0071] Preferably, the non-surfactant benefit agent has a hydrophilic index, and the first
surfactant has a hydrophilic index and wherein the hydrophilic index of the non-surfactant
benefit agent is within 0.5 and 2, or even within 0.7 and 1.5 or even within 0.8 and
1.2 times that of the hydrophilic index of the first surfactant.
[0072] The second surfactant has the general structure R'-E-C, wherein R' is a linear or
branched alkyl chain having a chain length of between 6 and 18 carbon atoms, E is
an ethoxy chain consisting of between 2 and 12 ethoxy groups and C is an end cap,
wherein the end cap is selected from;
- I. an alkyl chain consisting of between 1 and 8 alkoxy groups selected from propoxy
groups, butoxy groups and a mixture thereof; or
- II. an -OH group; or
- III. a linear or branched alkyl chain of the general formula R"H wherein R" consists
of between 1 and 8 carbon atoms;
- IV. or a mixture thereof.
[0073] The alkyl chain of the second surfactant may comprise between 8 and 16 or even between
10 and 14 carbon atoms.
[0074] The ethoxy chain of the second surfactant may consist of 3 to 10 or even 4 to 8 ethoxy
groups.
[0075] The weight ratio of the first surfactant to the second surfactant maybe from 5:1
to 1:8, or even from 3:1 to 1:7, or even from 2:1 to 1:6.
[0076] The alkyl alkoxylated surfactant of the treatment composition may comprise no more
than 50wt%, preferably no more than 40wt%, or 30wt%, or 20wt% or even no more than
10wt% of the total surfactant present in the unit dose article.
[0077] The liquid composition may comprise less than 2%, or even less than 1%, or even less
than 0.5% by weight of the composition of an anionic surfactant.
Solvent
[0078] The composition comprises between 0% and 40% by weight of the composition of a solvent,
wherein the solvent is selected from polar protic solvents, polar aprotic solvents
or a mixture thereof. Preferably, the solvent is selected from polar protic solvents.
[0079] Polar protic solvents are solvents that possess OH or NH bonds and can participate
in hydrogen bonding. Those skilled in the art will recognize suitable polar aprotic
solvents. Preferably, the polar aprotic solvent is selected from the group comprising
water, glycerol, monopropylene glycol, dipropylene glycol, ethanol, methanol, propanol,
iso-propanol and mixtures thereof.
[0080] Polar aprotic solvents are solvents that have a dielectric constant greater than
15 and do not contain OH or NH groups. Those skilled in the art will recognise suitable
polar aprotic solvents.
[0081] Preferably the solvent is selected from the group comprising water, glycerol, monopropylene
glycol and mixtures thereof.
Adjunct ingredients
[0082] The liquid composition may comprise an adjunct ingredient. Suitable adjunct ingredients
may be selected from polymers, surfactants, builders, dye transfer inhibiting agents,
dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach activators,
polymeric dispersing agents, anti-redeposition agents, suds suppressors, dyes, opacifiers,
additional perfume and perfume delivery systems, structure elasticizing agents, hydrotropes,
processing aids and/or pigments.
[0083] The liquid composition may comprise an aesthetic dye, an opacifier, an enzyme or
a mixture thereof.
[0084] The composition may comprise aesthetic dyes and/or pigments. Suitable dyes include
any conventional dye, typically small molecule or polymeric, used for colouring cleaning
and/or treatment compositions. These are generally non-fabric hueing dyes.
[0085] The composition may comprise a rheology modifier. The rheology modifier may be selected
from non-polymeric or polymericrheology modifiers. The rheology modifier may be a
non-polymeric rheology modifier, preferably a crystallisable glyceride. The rheology
modifier may be a polymeric rheology modifier, preferably a fibre based polymeric
rheology modifier, more preferably a cellulose fibre-based rheology modifier. The
rheology modifier may be selected from acrylate-based polymers including acrylate
homopolymers or acrylate containing co-polymers. The rheology modifier may be selected
from crystallisable glyceride, cellulose-fibre based structurants, TiO
2, silica and mixtures thereof.
[0086] The composition may comprise a pearlescent agent.
Method of making
[0087] The composition of the present invention may be made using any suitable manufacturing
techniques known in the art. Those skilled in the art would know appropriate methods
and equipment to make the composition according to the present invention.
[0088] The dimensions and values disclosed herein are not to be understood as being strictly
limited to the exact numerical values recited. Instead, unless otherwise specified,
each such dimension is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension disclosed as "40
mm" is intended to mean "about 40 mm."
EXAMPLES
[0089] The laundry treatment composition of the unit dose article of the present invention
was compared to a comparative composition.
[0090] Composition A according to the present invention was prepared as follows;
Composition A
1,2 Propane-diol |
7.6wt% |
Glycerol |
5.0 wt% |
alkyl alkoxylated alcohol (C 13-15 -EO -BO) commercially supplied as Plurafac LF223 |
27.3wt% |
alkyl branched ethoxylated alcohol (C10-EO4) commercially supplied as Lutensol XP40 |
40.0wt% |
Water |
5.9wt% |
linear alkyl ethoxylate hueing dye present as a 12wt% active in 1,2-propanediol |
10wt% |
Acrylate/styrene opacifier commercially available as OP305; 30wt% active in 1,2-propanediol |
4.2wt% |
[0091] Composition A was compared to commercially available Composition B which had the
following published formulation;
Composition B
water |
2 to 6 wt% |
1,2 PropaneDiol |
7 to 13 wt% |
Glycerine |
3 to 8 wt% |
Linear alkylbenzene sulphonic acid |
18 to 25 wt% |
Ethoxylated alkyl sulphate anionic surfactant |
7 to 14 wt% |
Non-ionic surfactant with an average degree of alkoxylation of 9 |
15 to 22 wt% |
Citric acid |
0.5 to 2 wt% |
Fatty acid |
5 to 9 wt% |
DTPA |
0.5 to 2 wt% |
PEI polymer |
4 to 9 wt% |
Minors |
1 to 3 wt% |
monoethanolamine (MEA) |
6 to 10 wt% |
alkyl ethoxylate hueing dye present as a 12wt% active solution of the hueing dye in
1,2-propanediol |
10 wt% |
[0092] For each composition, the following test was run;
- 1. Round, clean, white, cotton fabrics at the size of the well plate's cavity are
placed in 96-wellplate.
- 2. Pre-wet the fabrics using a very small volume of demin water.
- 3. Then pipette an excess amount (200uL) of the formulated products on top of the
pre-wetted fabrics.
- 4. Incubation at 25°C of the fabrics and formulated products for 45 mins.
- 5. After this, the formulated products are removed (pipetted off).
- 6. Any formulated product residues are washed off using a generic Liquid Laundry detergent
solution during a 15 mins wash cycle at 25C.
- 7. The wash water is fully removed (pipetted off).
- 8. Finally the fabrics are put through 3 short, consecutive rinse cycles (30secs each)
with demin water.
- 9. The rinse water is fully removed (pipetted off).
- 10. Wellplates are placed in the oven at 35degC to allow the fabrics to dry.
- 11. A picture of the wellplates holding the dry, stained fabrics is taken using the
Digi-Eye instrument.
- 12. Image analysis is performed to assess the discoloration of the fabric versus the
untreated fabrics (for e.g. delta E is reported).
[0093] A higher dE corresponds to a higher degree of staining. Results can be seen in Table
1 below
Table 1
Formula |
dE |
Composition A |
2.04 |
Composition B |
9.43 |
[0094] As can be seen from Table 1, Composition A according to the present invention exhibited
a lower dE and so resulted in a lower degree of fabric staining than comparative Composition
B.
[0095] The following are examples of laundry treatment compositions that can be formulated
in unit dose articles of the present invention. Preferably the following formulations
are formulated into a single compartment on a multicompartment unit dose article.
|
1 (wt%) |
2 (wt%) |
3 (wt%) |
4 (wt%) |
1,2 propane diol |
7.6 |
10.0 |
2.0 |
5.1 |
Glycerol |
5.0 |
5.0 |
1.0 |
8.0 |
Plurafac LF223 |
27.3 |
63.0 |
53.0 |
15.4 |
Lutensol XP40 |
40.0 |
10.0 |
27.0 |
50.0 |
Water |
5.9 |
2.0 |
3.0 |
7.0 |
alkyl ethoxylate hueing dye present as a 25wt% active solution of the hueing dye in
1,2-propanediol |
10.0 |
10.0 |
10.0 |
10.0 |
Acrylate/styrene opacifier commercially available as OP305; 60wt% active in 1,2-propanediol |
4.2 |
- |
4.0 |
4.5 |